Detergent composition



United States Patent 3,320,174 DETERGENT COMPGSETION Joseph Rubinfeld,Brooklyn, N.Y., assignor to Colgate- Palmolive Company, New York, N.Y.,a corporation of Delaware N0 Drawing. Filed Apr. 20, 1964, Ser. No.361,289 9 Claims. (Cl. 252-138) The present invention relates todetergent compositions comprising a mixture of higher linear alkylbenzene sulfonate detergents having particular characteristics ashereinafter described which exhibit a high level of performance.

The most widely used surfactant in household detergents for the past tenyears has been polypropylene tetramer branched :alkyl'benzene sulfonate.The advent of the importance of biodegradability dramatically shiftedthe emphasis from alkyl benzene sulfonate derived from polypropylene tolinear alkylate benzene sulfonates. For commercial utility, it isdesirable to develop an alkylate structure which would meet three majorrequirements. First, performance should be comparable with that ofpolypropylene benzene sulfonate. Secondly, the economics should be inthe same range and thirdly, it should be biodegradable. A main factorfor consideration is that of preparing linear alkyl benzene sulfonateswhich exhibit a high level of performance when used in conjunction withinorganic builder salts in dishwashing and laundering compositions.

The problem of changing from polypropylene benzene sulfonate basedformulations arises due to the fact that it is known that theconventional commercial polypropylene benzene sulfonates areparticularly resistant to biological degradation by bacteria normallypresent in microorganism populations of activated sewage sludge (andthat they are not otherwise removed by adsorption, etc.). Thus, it isknown that severe foaming and frothing have occurred in rivers andstreams into which sewage disposal plants discharge their efiluent. Ithas now been found that the detergent material of the type described inthis invention remedies the foregoing problem because it is readilyremoved by degradation or adsorption on the sludge and when processed ina sewage plant produces an etlluent from said plant having little or notendency to foam and furnishes a high level of performance as hereindescribed.

The present invention relates to detergent compositions comprisingessentially a mixture of higher alkyl benzene sulfonates, the alkylatedbenzene content of said sulfonates having an average molecular weightwithin the range of 250 to 270, and particularly from 252 to 266, saidalkyl groups being essentially linear and containing a minimum of about85% and particularly 90% of alkyl groups having 12 to 14 carbons with atleast about 10% and particularly at least about 15% each of dodecyl,tridecyl and tetradecyl groups, said alkyl benzene sulfonates having aminimum of about 37% of S-phenyl and higher phenyl isomers and a maximumof 27% of 2-phenyl isomers, said :amounts being by weight. A feature ofthe present invention resides in detergent compositions comprising aminor proportion of said sulfonates admixed with a major amount ofwater-soluble inorganic builder salts, particularly alkaline buildersalts. Various other features will be apparent in the followingdescription.

The detergent compositions of the present invention are characterized bymany desirable properties. The particular linear alkyl benzene sulfonatesalts result in detergent compositions which exhibit optimum cleansingand foaming properties, particularly in admixture with neutral detergentbuilder salts or alkaline builder salts. The use of the particularblends or mixtures of linear "ice sulfonates herein described result inbuilt detergent compositions which exhibit over-all superiorcharacteristics as compared with the standard polypropylene derivedtridecyl benzene sulfonate under the same conditions. In addition, theclaimed linear alkyl benzene sulfonates having the desired structuralcharacteristics exhibit markedly superior properties as compared withother linear alkyl benzene sulfonate mixtures not having the specifiedstructural properties evaluated under the same conditions. The detergentcompositions exhibit superior foaming properties in the presence ofgreased soil in the dishpan and a high level of washing power in thelaundering of soiled textiles. In addition, the foaming power isenhanced in hard water where washing conditions are most demanding. Theimproved foaming, detergency and emulsification properties of thespecific linear alkyl benzene sulfonates in heavy duty detergentcompositions in both hard and soft water is particularly significant incomparison with the other linear phenyl alkane sulfonate detergents.

The desired linear alkyl benzene materials should be characterized bythe proper relationship and integration of various factors to providefor optimum performance of the corresponding sulfonate detergents. Ithas been found that the molecular Weight, the proportion of ndodecyl,tridecyl and tetradecyl alkyl groups and character of the isomer contentsuch as the phenyl position isomers mutually affect one another andprovide a criterion for the determination and selection of thosesulfonate materials which result in superior performance of the ultimatedetergent composition. For convenience of illustration, these factorsare discussed individually below to some extent, but the desiredproperties result from the proper integration thereof. As indicated, themolecular weight is an important consideration. In general, the linearalkyl benzene portion of said sulfonates should have a mean molecularweight within the range of 250- 270, preferably 252266, and particularlyfrom 255 to 262 for optimum effects. In conjunction with the molecularweight, the distribution of the carbon chains in the linear alkylbenzene structure is another important consideration. For example,structures within the specified molecular weight range should contain atleast about and preferably at least about of carbon chains as C C and Cwith less than 15% and preferably less than 10% of other alkyl chainssuch as C and lower and C and higher chains. Further, the minimumproportion of each of the dodecyl, tridecyl and tetradecyl alkyl chainsshould be about 10%, and preferably 15%. A preferred distribution ofcarbon chains is about 2040% C about 30-50% C and about 20-40% of Calkyl chains. A third factor to be considered in optimizing theperformance characteristics of the corresponding sulfonates is thedistribution of phenyl isomers. For example, it has been found that themixed chain linear alkyl benzene sulfonate materials containingparticular proportions of internal 5- and 6'phenyl isomers are betterfoaming materials under a variety of conditions than mixtures containingpredominately the 2, 3 and 4 phenyl isomers. Therefore, to achieve thedesired char acteristics in the detergent compositions a minimum of 37%of 5-, 6- and higher phenyl isomers and a maximum of 27% of the 2-phenylalkane should be present for the proper performance characteristics.Preferred phenyl alkane distributions should contain the maximum 5-, 6-and higher phenyl alkane and the minimum 2- phenyl alkane consistentwith economic production techniques. From the practical manufacturingstand-point, such mixtures can be made on a particularly economic basiswith a 5-, 6- and higher phenyl content within the range of 3760% andthe 2-phenyl content within the range of 5 to 27%. Examples ofparticularly suitable linear alkyl benzene materials have the followingapproximate chemical characteristics:

A B O D E Molecular weight 256 256. 8 256. 7 255. 6 255. 6 Alkyl chainsin the C 014 range, percent 93. 3 94. 7 98. 4 91. 2 93. 2

Percent G 34. 5 35. 1 33.8 34. 36. 0 Percent C 42. 8 43. 4 50. 2 32. 735. 8 Percent C 4 16.0 16. 2 14. 4 24. 5 21. 4

2 phenyl alkane, percent. 19. 1 18. 6 2G. 4 24. 8 25.6 5, 6 and higherphenyl alkane, percent 39. 7 43.1 37.1 37. 3 38. 3

Carbon chain content is expressed as mole percent.

The linear alkyl benzene sulfonate detergents having the describedessential structure can be produced by sulfonating the correspondingalkyl benzene hydrocarbons. These hydrocarbons are obtained byalkylating benzene with linear alkyl materials having the requiredmolecular weight and distribution of alkyl carbon chains. In general,linear alkyl halide, l-alkene or linear primary and secondary alcoholhaving the specified carbon chain distribution and molecular weight isalkylated with benzene in the presence of a Friedel-Crafts typecatalyst, usually aluminum chloride, hydrogen fluoride or sulfuric acid,to form the desired linear alkyl benzene material. The products aresulfonated in known manner with a sulfonating agent, such as 20% oleumor sulfur trioxide at 90 F., and neutralized with alkali to form thecorresponding water-soluble higher alkyl benzene sulfonate detergentsalts. It is preferred to use the alkali metal salts such as the sodium,potassium and lithium salts although other highly soluble salts such asthe ammonium, and lower alkylolamine, e.g. monoand tri-ethanolamine,salts may be employed also. The corresponding calcium and magnesiumsalts are prepared similarly. In addition, the product may containvarying amounts of water-soluble inorganic sulfate salts resulting fromthe neutralization of any excess sulfuric acid employed in thesulfonation reaction.

In more detail, the linear alkyl chain may be derived from kerosene bydistillation to yield a fraction containing C -C hydrocarbons, such ascontaining about 34% dodecyl, 43% tridecyl and 17% tetradecyl alkylchains. The desired linear alkyl fraction may then be reacted with ahalogen in a monohalogenation reaction process to yield a mixture ofkerosene and monohalogenated kerosene which can be separated in asubsequent distillation. The halogenated kerosene fraction contains thehalogen randomly distributed along the alkyl chain and is generallyalkylated with benzene in the presence of aluminum chloride catalyst.The typical product of such alkylation reaction consists of an isomericmixture of phenyl alkanes of the desired chain length containing usuallya relatively high proportion of 2-phenyl alkane and relatively lowproportions of other isomers as analyzed by mass spectrometry. Becausethe linear alkyl benzene product from this reaction contains generally ahigh content of the 2-phenyl alkane, it is necessary to carry out ablending operation or additional processing operations in order toreduce the 2-phenyl isomer concentration to the desired level. Forexample, subsequent distillation concentrates the Z-phenyl isomer in thebottoms with simultaneous increases in the higher phenyl isomers. Theconcentrated 2-phenyl alkane material can be then recycle to thealkylation reactor wherein rearrangement of the phenyl position occursduring the subsequent equilibrium alkylation reaction in the presence ofthe aluminum chloride catalyst.

Alternatively, use of alpha olefins having the desired distribution ofcarbon chains in the alkylation reaction with benzene in the presence ofhydrogen fluoride catalyst under proper conditions may have certainadvantages. The hydrogen fluoride catalyst is a rate controllingcatalyst 4 and the resulting product contains generally a mixture of 2-,3-, 4-, 5-, 6- and 7-phenyl alkane which can be treated to obtain afinal product of any desired proportions.

Alkylation processes involving use of sulfuric acid catalyst result inmixtures of isomeric phenyl alkanes containing usually a highpredominance of 2-phenyl alkane, and lesser amounts of the otherisomers. Therefore, this product generally requires additionalprocessing operations analogous to the aluminum chloride catalyzedalkylation product such as by blending or distillation to reduce the2-phenyl alkane to the desired level.

For detergent use, these new alkyl aryl sulfonate detergent mixtures areadvantageously used in combination with detergent builders. Suchbuilders are generally watersoluble inorganic salts which may be neutralbuilder salts such as sodium sulfate, alkaline builder salts such assodium tripolyphosphate or mixtures of the neutral builder salts andalkaline builder salts. Typical examples of other suitable inorganicbuilder salts, preferably alkali metal salts, are sodium and potassiumcarbonate, tetrasodium pyrophosphate, trisodium phosphate, sodium andpotassium tripolyphosphate, sodium hexametaphosphate and sodium andpotassium silicates, such as sodium metasilicate (Na O:SiO and alkalinesodium silicates (Na O:2SiO and Na O:3SiO It is in many casesadvantageous to add one or more phosphates and one or more silicates incombination.

If desired, the compositions according to the invention may also containother detergent adjuvant materials. Soilsuspending agents which areusually cellulosic or starch derivatives may be used, preferably thesodium salt of carboxymethylcellulose. Other components which may beadded as desired in suitable amounts to the compositions according tothe invention are bleaching agents, i.e., agents which have an oxidizingeffect, and optical bleaching agents, the effect of which is due tofluorescence. In particular, peroxygen compounds such as persulfates,perborates and percarbonates, for example, are suitable as chemical,i.e., oxidizing, bleaching agents. Various organic materials intended tomodify the foaming or cleansing power may be added such as lauric orcoconut diethanolamide, monoethanolamide, isopropanolamide and ethyleneoxide derivatives thereof, fatty alcohols such as lauryl or cetylalcohol, amine oxides such as dodecyl dimethyl amine oxide, and thelike. Solubilizing agents such as the commercial sodium and potassiumXylene and toluene sulfonates may also be included where desired.

The new compositions can also contain other surfaceactive agents besidesthe alkyl aryl sulfonates of the invention. More preferably, these maybe of the anionic and/ or nonionic type. Alkyl sulfonates and alkylsulfate salts having alkyl chains of 8 to 2-0 carbon atoms are typicalof the anionic surface-active agents which can be used as well as alkylaryl sulfonates which do not have the advantageous structure of the newcompounds. Other suitable anionic materials are the sulfated higheralkyl phenol-ethylene oxide condensates and the sulfated higher alkylethylene oxide sulfates, preferably containing an average of about 1-10moles of ethylene oxide. Polyethylene glycol ethers and esters areexamples of suitable nonionic surface-active agents which can beadvantageously used in the new compositions.

Formulations containing these specific linear alkyl benzene sulfonatesalts in combination with inorganic detergent builder salts may be ofthe light duty type containing only neutral builder salts or of theheavy duty type containing a substantial amount of alkaline buildersalts, or mixtures of alkaline and neutral builder salts. Theproportions of the various components can be varied depending upon thetype of washing formulation. Generally, both types of composition willcontain a minor proportion, e.g. 150'%, usually 5 to 50% by weight andpreferably 1535% by weight, of the specific linear alkyl benzenesulfonate surface active agent and a major proportion, e.g. 50-99%,usually 50-95% by weight and preferably 65-85% by weight, of theinorganic builder salts. Where heavy duty formulations are prepared fromabout to about 90% by weight, preferably 33-70% by weight, of theinorganic builder salts may consist of the inorganic polyphosphates suchas sodium tripolyphosphate. The above amounts are by weight of thespecified mixture of ingredients.

A significant feature of the foregoing compositions is that theparticular linear alkyl benzene sulfonates represent optimum foamingperformance properties in varying water hardnesses as compared withother linear alkyl benzene sulfonate mixtures under similar washingconditions when admixed with either neutral inorganic builder salts oralkaline builder salts. The built detergent composition within thedescribed proportions also exhibits more foam in hard than in softwater.

The detergent composition may be prepared in any suitable form, eitheras liquids, pastes or as solid product in cake (e.g. bar or tablet) orin particulate form. The described linear alkyl benzene sulfonates maybe the sole active ingredient or admixed with other suitable materialsas indicated. It is prepared preferably in particulate form by theapplication of known heat-drying procedures on an aqueous mixture of thesulfonate salts with or without the presence of the inorganic builders.Thus, an aqueous mixture of the sulfonates may be roll-dried, drum-driedor spray-dried in known manner at a temperature above 212 F. to produceparticles in the form of flakes or beads. Alternatively, the materialsin substantially solid form may be admixed mechanically in known mannerto form a uniform mixture. Furthermore, the ingredients in solid formmay be admixed with sufficient water which will be absorbed byhydratable inorganic salts to form a substantially dry product which canthen be ground or sieved to size as desired. In the preparation ofliquid products in clear, translucent or opaque form, there may be addedvarious solubilizing materials in suitable amounts such as ethanol,propylene glycol, urea, hydrotropic salts such as sodium and potassiumcommercial xylene and toluene sulfonates, added foaming modifiers suchas the higher fatty acid alkylolamides, builder salts in suitableproportions such as tetrapotassium pyrophosphate, other compatibledetergents, etc.

As stated earlier, evaluation data obtained with both light dutydetergent compositions and heavy duty detergent compositions illustratethe unusual characteristics of the product. For example, various typicalheavy duty detergent compositions were prepared as herein describedcontaining about 24% of sulfonate detergent active inthe number ofplates washed before the disappearance of the foam.

The general effect of substituting various linear alkyl benzenesulfonates for a polypropylene-derived tridecyl benzene sulfonate insaid detergent composition is clearly indicated in the following tableusing the aforementioned dishwashing evaluation test, the linearsulfonates all having a Z-phenyl content of about 30%.

TABLE I Number or Plates Linear ALryl Benzene Mean Molecular WashedSullonate Weight p.p.m. 150 ppm.

242 9 15 256 14 17 257 15 17 263 15 17 273 12 13 285 12 11Trideeylbenzene sulfonate from polypropylene 20 20 It is to be notedthat all of the linear alkyl benzene sulfonates gave substantiallypoorer performances than the standard tridecylbenzene sulfonate and alsothat the molecular weight is not a sufficient criterion per se ofproducts exhibiting optimum performance.

Further, evaluation of various linear alkyl benzene sulfonates havingthe described characteristics in the afore The above results clearlyindicate that the desired molecular weight range combined with a lower2-phenyl content results in improved performance.

The contribution of carbon chain length is similarly indicated in theevaluation results of a pair of linear alkyl benzene sulfonates having a2-phenyl content of about 1' o O 3 0 in said heavy duty composition asfollows:

TABLE III Alkyl Distribution* Number of Plates Linear Alkyl Mean WashedBenzene Sultanate Molecular Weight 0-12 0-13 0-14 50 ppm. 150 p.p.m.

*Alkyl distribution is expressed in mole percent.

gredient as sodium salts, about 35% sodium tripolyphosphate, about 7%sodium orthosilicate, about 29% sodium sulfate and about 5% moisture.The sulfonate in rolldried form was mixed with the other ingredients anddissolved in water to form aqueous washing solutions which weresubjected to foam stability tests in a practical dishwashing procedure.In this test, all products are examined at 0.15% concentration, at 115F. and at 50 and 150 ppm. hardnesses, employing a layer of hydrogenatedvegetable oil type of soil on each plate. The soiled plates are washedby hand continuously until the foam has collapsed in the wash water ineach case, furnishing a com- These result-s illustrate the influence ofchain contributions, being essentially independent of phenyl positionand molecular weight. In particular, the redistribution of C- 13 contentinto C-11 and C-15 homologs materially lowers the performance.

Similar evaluation results of the detergent composition are set forth inthe following table which clearly illustrate the effect of controllingthe proportion of 2-phenyl isomers in said linear alkyl benzenesulfonates having the preferred mean molecular weight of 256 and thepreferred carbon chain length in the described heavy duty parison of thefoam stability of each washing solution in detergent composition.

TABLE IV Number of Plates Linear Alkyl 2-Pheny1 Washed Benzene Sulfo-Content -11 0-12 C-13 0-14 C-15 nate (percent) 50 p.p.m. 150 p.p.m.

P r 34 4. 5 33.9 43. 0 15. 7 2. 3 14 15 A 19 4. 8 34. 5 42. 8 16. 0 1. 219 22 The two linear alkyl benzene sulfonates above-described arecomposed of essentially identical alkyl chain distributions, therebyeffectively making the sole variable the phenyl position. Theimprovement in dishwashing performance shown in this table therefore isattributable to the effects of phenyl position alone.

The importance of the phenyl isomer distribution, namely minimizing theamount of 2-phenyl and maximizing the amount of 5-, 6- and higher phenylin the linear alkyl benzene sulfonates, is illustrated again in thefollowing table. The linear alkyl benzene sulfonates containing only 4-and higher phenyl isomers and having the desired molecular weight andphenyl isomer distribution were evaluated in the described heavy dutydetergent formulation using the described dishwashing test.

*Alkyl distribution is expressed in weight percent.

The foregoing data clearly show that foaming and emulsificationproperties of detergent compositions containing the biodegradable linearalkyl benzene sulfonate salts having the claimed characteristics aresuperior to polypropylene benzene sulfonate materials.

Similar results are also obtained in water of varying hardness for thedescribed linear alkyl benzene sulfonate salts in light duty detergentcompositions, a typical formulation comprising about 31% of saidsulfonate detergent mixture, 67% sodium sulfate and 2% moisture.

The following examples are additionally illustrative of the presentinvention and all amounts are by weight unless otherwise specified.

Example I .-Preparation of the sodium linear alkyl benzene sulfonatesThe sodium linear alkyl benzene sulfonates above-described are preparedby the following typical procedure. The selected alkylates are reactedwith benzene using aluminum chloride or hydrogen fluoride catalyst inknown manner to obtain the desired alkylated benzene product. Thesematerials are sulfonated using a standard oleum batch sulfonatetechnique wherein 525 grams of oleum are added to 500 grams of linearalkyl benzene with agitation over the period of about 30 minutes whilemaintaining the temperature of the reaction at 90:5 F. using a coldwater bath. The sulfonation reaction mixture is then heated to 120122 F.and maintained at this temperature for about 90 minutes to complete thesulfonation reaction. The acid mixture is then diluted with distilledwater in a ratio of 10.8 parts of water per 100 parts of acid mix whileagitating the mixture and cooling to maintain the temperature at about130135 F. The diluted acid mix is then allowed to separate by gravityinto a sulfonic acid rich upper layer and a sulfuric acid rich lowerlayer while maintaining the temperature at about 135i5 F. or centrifugedinto tWo layers. The sulfonic acid layer containing about 88% sulfonicacid, 7% sulfuric acid and 5% water is then neutralized by adding slowlyto 15-20% sodium hydroxide solution while maintaining the temperature at120:5 F. using cooling water bath to yield a neutralized alkyl benzenesulfonate slurry of pH 9.5105 containing about 4550% solids by weight.The neutralized alkyl benzene sulfonate slurry is then roll-dried usinga two roll mill while maintaining 15 p.s.i.g. steam on the interior ofthe rolls to yield a dried sulfonate product in flake form of about 90%purity, the balance being sodium sulfate formed by neutralization of theexcess sulfuric acid. It is unnecessary to remove said minor amount ofsodium sulfate but, if desired, a suitable purification technique is todilute the neutralized slurry with an equal volume of ethanol whereinthe sodium sulfate precipitates. The alcoholic layer containing thesulfonate is then drum dried to yield a sulfonate of 98% purity. Thesodium linear alkyl benzene sulfonates of the present invention such asmixtures A-E in Table II above exhibit a high level of cleansing andfoaming ability in dishwashing and laundering and have been found to bebiodegradable.

In similar manner, the aqueous slurries may be neutralized with alkaliother than caustic soda in known manner to form the potassium, ammonium,triethanolamine, calcium and magnesium salts of said linear alkylbenzene sulfonates and mixtures thereof which are effective detersivematerials also.

Examples 11-111 The sodium linear alkyl benzene sulfonates in flake formare admixed with inorganic salts according to the following formulationsto form light-duty product 11 and heavy-duty product III:

The sulfonates in roll-dried form are blended with the solid powderedinorganic builder salts to yield a particulate solid product.

As described, these products exhibit particularly satisfactoryperformance and are biodegradable also.

Example IV The neutralized aqueous slurry of sodium linear alkyl benzenesulfonate C was prepared in spray-dried form having the followingcomposition:

Ingredients: Percent Sodium linear alkyl benzene sulfonate C 24.8 Sodiumtripolyphosphate 35.0 Sodium sulfate 24.0 Sodium silicate 7.0 Sodiumcarboxymethylcellulose 0.4

9 Ingredients: Percent Polyvinyl alcohol 0.2 Fluorescent brighteners 0.2Anti oxidant, perfume, anti tarnishing agent 0.3 Moisture 8.1

The above ingredients are mixed at about 160 F. in a soap crutcher toform an aqueous slurry of about 60% solids. This slurry is submitted tospray-drying with heated air at a temperature of about 650 F. with aresultant moisture loss of almost 35%. The final product is recovered inthe form of beads and possesses a high degree of detersive and foamingproperties in both soft and hard water in dishwashing and laundering andis biodegradable after use.

Other particularly satisfactory spray-dried detergent compositionscontaining the specified linear alkyl benzene sulfonate are set forth inExamples V and VI which follow:

Example Indredient;

sodllllgn linear alkyl benzene sulfonate Sodium salt of mixe tty acids(85% tallow/l5% coconut) Sodium tripolyphosphate Sodium silicate (ratioof NazOzSiOz= 1:2.35) Sodium sulfate Sodium carboxymethylcellu Moistureoco . cannot Example VIl.Abrasive cleanser Ingredients PercentSpray-dried detergent particles of Ex. IV l0 Silica (fine particle sizeof less than 200 mesh) 90 Minor amounts of suitable bleaching agentssuch as 0.25% of trichlorocyanuric acid or chlorinated trisodiumphosphate or 0.5% of oxalic acid as an oxidizing agent may be added inpowdered form.

Although the present invention has been described and illustrated withreference to specific examples, it is understood that modifications andvariations of composition and procedure are contemplated within thescope of the appended claims.

Having thus described the invention, what is claimed is:

1. A detergent composition consisting essentially of a mixture of higheralkyl benzene sulfonates, the alkylated benzene content of saidsulfonates having an average molecular weight within the range of 250 to270, said alkyl groups being linear and containing a minimum of about85% of alkyl chains of 12 to 14 carbons with at least about having 12carbon atoms, at least about 10% having 13 carbon atoms and at leastabout 10% having 14 carbon atoms, said alkyl benzene sulfonates havingphenyl isomers in at least one of the 2- and higher positions of saidalkyl groups, said phenyl isomers being a minimum of about 37% ofS-phenyl and higher phenyl isomers and a maximum of about 27% of2-phenyl isomers, said amounts being by weight.

2. A detergent composition consisting essentially of a mixture ofWater-soluble higher alkyl benzene sulfonates, the alkylated benzenecontent of said sulfonates having an average molecular weight within therange of 252 to 266, said alkyl groups being linear and containing aminimum of about 90% of alkyl chains of 12 to 14 carbons with at leastabout 15% having 12 carbon atoms,

at least about 15% having 13 carbon atoms and at least about 15% having14 carbon atoms, said alkyl benzene sulfonates having phenyl isomers inat least one of the 2- and higher positions of said alkyl groups, saidphenyl isomers being a minimum of about 37% of 5-phenyl and higherphenyl isomers and a maximum of about 27% of 2-phenyl isomers, saidamounts being by weight.

3. A detergent composition in accordance with claim 2 wherein said alkylgroups of 12 to 14 carbon has a carbon chain distribution of about20-40% of 12 carbon, about 30 to 50% of 13 carbon and about 20 to 40% of14 carbon alkyl chains.

4. A detergent composition in accordance with claim 2 having a 5-phenyland higher isomer content from 37-60% and a 2-phenyl content from 5 to27%.

5. A detergent composition in accordance with claim 1 wherein saidmixture of higher alkyl benzene sulfonates is about 150% of saidcomposition and about 5099% of said composition is water-solubleinorganic salts selected from the group consisting of neutral buildersalts, alkaline builder salts and mixtures thereof, said amounts beingby weight of the above materials.

6. A detergent composition in accordance with claim 2 wherein saidmixture of higher alkyl benzene sulfonates is about 550% of saidcomposition and about 5095% of said composition is water-solubleinorganic builder salts selected from the group consisting of neutralbuilder salts, alkaline builder salts and mixtures thereof with about1090% of said builder salts being p-olyphosphate salts, said amountsbeing by weight of the above materials.

7. A detergent composition in accordance with claim 6 wherein said alkylgroups of 12 to 14 carbon has a carbon chain distribution of about20-40% of 12 carbon, about 30 to 50% of 13 carbon and about 20 to 40% of14 carbon alkyl chains.

8. A spray-dried detergent composition consisting essentially of about150% of sodium higher alkyl benzene sufonates, the alkylated benzenecontent of said sulfonates having an average molecular weight within therange of 250 to 270, said alkyl groups being linear and containing aminimum of about of alkyl chains of 12 to 14 carbons with at least about10% having 12 carbon atoms, at least about 10% having 13 carbon atomsand at least about 10% having 14 carbon atoms, said alkyl benzenesulfonates having phenyl isomers in at least one of the 2- and higherpositions of said alkyl groups, said phenyl isomers being a minimum ofabout 37% of S-phenyl and higher phenyl isomers and a maximum of about27% of 2-phenyl isomers, and 5099% of water-soluble inorganic buildersalts selected from the group consisting of neutral builder salts,alkaline builder salts an mixtures thereof, said amounts being by weightof the above materials.

9. A detergent composition in accordance with claim 2 wherein the loweraverage molecular weight of the alkylated benzene content of saidsulfonates is an average molecular weight of 255.

References Cited by the Examiner UNITED STATES PATENTS 2,712,530 7/1955Baumgartner 252-161 2,944,028 7/1960 Stayner 252161 3,169,987 2/1965Bloch.

FOREIGN PATENTS 1,272,254 10/ 1960 France.

OTHER REFERENCES Swisher, Straight Chain ABS Biodegradation, Soap andChemical Specialties, July 1963, pp. 47-50 and 95.

LEON D. ROSDOL, Primary Examiner.

S. E. DARDEN, Assistant Examiner.

1. A DETERGENT COMPOSITON CONSISTING ESSENTIALLY OF A MIXTURE OF HIGHERALKYL BENZENE SULFONATES, THE ALKYLATED BENZENE CONTENT OF SAIDSULFONATES HAVING AN AVERAGE MOLECULAR WEIGHT WITHIN THE RANGE OF 250 TO270, SAID ALKYL GROUPS BEING LINEAR AND CONTAINING A MINIMUM OF ABOUT85% OF ALKYL CHAINS OF 12 TO 14 CARBONS WITH AT LEAST ABOUT 10% HAVING12 CARBON ATOMS, AT LEAST ABOUT 10% HAVING 13 CARBON ATOMS AND AT LEASTABOUT 10% HAVING 14 CARBON ATOMS, SAID ALKYL BENZENE SULFONATES HAVINGPHENYL ISOMERS IN AT LEAST ONE OF THE 2- AND HIGHER POSITIONS OF SAIDALKYL GROUPS, SAID PHENYL ISOMERS BEING A MINIMUM OF ABOUT 37% OF5-PHENYL AND HIGHER PHENYL ISOMERS AND A MAXIMUM OF ABOUT 27% OF2-PHENYL ISOMERS, SAID AMOUNTS BEING BE WEIGHT.